CN104411736A - New reactive polymer catalysts for 2-component epoxy resin systems - Google Patents
New reactive polymer catalysts for 2-component epoxy resin systems Download PDFInfo
- Publication number
- CN104411736A CN104411736A CN201380013786.4A CN201380013786A CN104411736A CN 104411736 A CN104411736 A CN 104411736A CN 201380013786 A CN201380013786 A CN 201380013786A CN 104411736 A CN104411736 A CN 104411736A
- Authority
- CN
- China
- Prior art keywords
- phenol
- hydroxymethyl
- condensation product
- polyamines
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
- C08G59/623—Aminophenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention describes an oligomeric condensation product that can be obtained from at least one (hydroxymethyl)phenol of general formula (I), in which R1 is hydrogen or -CH3, R2 is -CH2OH, and R3 is hydrogen or -CH3, at least one polyamine, and optionally at least one phenol compound having two centres reactive by means of a reaction with the methylol groups of the (hydroxymethyl)phenol. Condensation products of this type can be used as polymerisation catalysts for epoxy resins, wherein a quicker curing time with comparable pot life can be achieved in 2-component epoxy resin adhesives. It is thus possible to further reduce the manufacturing times in industrial application and to develop new fields of application, in which adhesive bonding can be applied instead of a screwed connection. The above-described condensation products also have the advantage compared to similar conventional condensation products that, in the event of synthesis of these products, no toxic substances such as formaldehyde or dimethylamine have to be used or are released. The present invention also relates to a method for producing the aforementioned oligomeric condensation compounds and to the use thereof in the curing of epoxy resin systems.
Description
The present invention relates to novel Mannich class condensation product and novel preparation method thereof.Another theme of the present invention is described condensation product purposes as promotor in the solidification of epoxy-resin systems.
Background technology
Epoxy resin is made up of polyether polymer, and described polyether polymer is formed according to reaction process when adding suitable solidifying agent has high strength and chemical-resistant thermosetting resin.When epoxy resin and solidifying agent mixing, be usually cured in several minutes to a few hours according to composition and temperature initial viscosity mixture.As the solidifying agent for epoxy resin, commercially different systems, such as based on the solidifying agent of amine, acid amides and acid anhydrides (such as with title
derive from Hexion Speciality Chemicals's) or based on the solidifying agent of polyetheramine (such as with title
derive from Huntsman's).
Also the Mannich base being derived from primary amine, formaldehyde and phenol can be used as solidifying agent or promotor (see EP 0 253 339 A).
WO 00/15687 describes by carrying out Mannich base promotor prepared by transamination with amine to Mannich base.
A shortcoming of conventional Mannich base is to use phenol as parent material, because these Mannich bases comprise the phenol of non-complete reaction usually.Due to the toxicity of free-phenol, therefore the Mannich base based on phenol is not suitable for many Application Areass.
Use another shortcoming of conventional Mannich base to be, Mannich base must obtain by using formaldehyde.Formaldehyde causes occurring allergy, chafing, respiratory inflammation and eye inflammation especially.Therefore need to provide and can avoid using formaldehyde and obtained Mannich class condensation product.
US 6,916,550 describes the scheme avoiding using formaldehyde, sets out and makes itself and diamines, particularly isolate dimethylamine with polyoxyalkylene diamine reactant simultaneously from 2,4,6-tri-(dimethylaminomethyl) phenol.But the shortcoming that described method has is, the dimethylamine produced also is virose (MAK-value 2ppm).Even if therefore can not avoid the release of the discharge be harmful to health according to the program.
In addition, the method for the preparation of Mannich base of the prior art is expensive especially time-consuming and be difficult to carry out, particularly when avoiding the formation of high molecular condensation product.Such as, EP 1 475411 discloses the two step method for the preparation of the Mannich base based on m-cresol or 3,5-xylenol and polyamines, wherein preferably uses tertiary amine.Also disclosing the two step method for the preparation of Mannich base in EP 1 475 412 A, wherein obtaining Mannich base when using tertiary amine by phenol (such as m-cresol, 3,5-xylenol or Resorcinol) and polyamines.This two step method concerns significant cost and makes the preparation of Mannich base become expensive.
In addition, EP 0 292 701 describes the reaction product of two (the methylol)-p-cresol of Guayule resin and polyether diamine and 2,6-.In order to prepare described reaction product, Guayule resin composition is with relative to polyether diamine and 2, the amount use that two (the methylol)-p-cresol of 6-is significantly excessive, thus obtain the mixture of the reaction product of the polyethers of amine end-blocking and the reaction product of Guayule resin and two (the methylol)-p-cresols of another aspect 2,6-and Guayule resin on the one hand.Advise the additive of described reaction product as rubber product.
US 2003/0187155 A1 describes the epoxy hardener system for solidifying at low temperatures., wherein between each composition, there is not covalent linkage in the mixture of this curative systems is in particular 2,6-two-(methylol)-p-cresol, tetramethyl guanidine and TriMethylolPropane(TMP).
WO 02/42349 A2 describes the solidifying agent for epoxide composition equally, and described epoxide composition can be made up of the mixture of amine and polyphenol.In the embodiment of the document, particularly describe two (the methylol)-p-cresol of 2,6-and tetramethyl guanidine with the combination of composite form.Such as in US 2003/0187155A1, described in be combined as the molecular complex of described composition.
According to an alternative, such as, described in EP 717 253 A1, Resorcinol can be used as phenol initial product, Resorcinol is provided for the lower molecular weight Mannich base of the solidification of epoxide composition when reacting with formaldehyde and polyamines.
From prior art, the object of the present invention is to provide the substituting promotor for epoxy resin that overcomes above-mentioned shortcoming as far as possible or the solidifying agent for epoxy resin and urethane.Especially, the object of the present invention is to provide the promotor for epoxy resin or the solidifying agent for epoxy resin and urethane, it does not on the one hand comprise free-phenol and not release formaldehyde and other toxicant, such as dimethylamine as much as possible in the preparation on the other hand.Therefore the parent material using phenol and formaldehyde and discharge toxicity amine (such as dimethylamine) when reacting with polyamines preferably should be abandoned when preparing corresponding promotor.
Summary of the invention
Realize described object by a kind of oligomeric condensation product, described oligomeric condensation product can by (hydroxymethyl) phenol of at least one general formula (I), at least one polyamines and optionally at least one phenolic compound be obtained,
Wherein R
1represent hydrogen or-CH
3, R
2expression-CH
2oH, and R
3represent hydrogen or-CH
3, described phenolic compound has two reactive centers for the reaction of the methylol with (hydroxymethyl) phenol.
Oligomeric condensation product according to the present invention is suitable as the promotor of epoxy-resin systems and as the solidifying agent for epoxy-resin systems (particularly with the form of bicomponent epoxy resin system) and urethane.Compared to the suitable solidifying agent of prior art, set time and suitable working life fast can be obtained in two component epoxy compound tackiness agent.Therefore shorten manufacturing time, this opens up the possibility of new Application Areas, tackiness agent wherein can be used to substitute bolt and connects or rivet interlacement.
Oligomeric condensation product according to the present invention is particularly suitable for the solidification promoting epoxy resin binder, for improvement of the adhesivity of epoxy resin binder and/or the shearing resistance of epoxy resin binder, wherein owing to using specific phenol component and amine component, substantially avoid shortcoming well known in the prior art.Especially, oligomeric condensation product according to the present invention does not comprise the resistates of phenol, formaldehyde or other toxicant such as dimethylamine.
Oligomeric condensation product according to the present invention is by simply obtaining by simple preparation method with cheap raw material, and described preparation method describes hereinafter and is theme of the present invention equally.According to the feature of the oligomeric condensation product of the present invention outstanding curing action particularly in epoxy resin binder.
As mentioned above, the present invention relates to oligomeric condensation product, described oligomeric condensation product by least one according to (two-hydroxymethyl) phenol of general formula (I), at least one polyamines and optionally at least one phenolic compound obtain, described phenolic compound has two reactive centers for the reaction of the methylol with (two-hydroxymethyl) phenol.
In scope, (hydroxymethyl) phenol is understood to be in the ortho position of phenol OH-group, a position or the contraposition phenol with at least one hydroxymethyl substituents.Described phenol commercially.Preferably such (hydroxymethyl) phenol, wherein R
2the ortho position of phenol OH-group is positioned in formula (I).In a substituting preferred embodiment, (hydroxymethyl) phenol of general formula (I) has at least one other CH
3-group is base R alternatively
1or R
2.Preferably (hydroxymethyl) phenol is 2,6-bis-(hydroxymethyl)-4-methyl-phenol and 2,4-bis-(hydroxymethyl)-6-methyl-phenol.For cost reason, particularly preferably use 2,6-bis-(hydroxymethyl)-4-methyl-phenol.
In this external scope, also other (hydroxymethyl) phenol can be added according to oligomeric condensation product of the present invention in order to prepare, such as 2-(hydroxymethyl) phenol, 3-(hydroxymethyl) phenol or 4-(hydroxymethyl) phenol, but other (hydroxymethyl) phenol described should account for the highest 50 % by mole, particularly the highest 20 % by mole and particularly preferably the highest 10 % by mole of the total amount of (hydroxymethyl) phenol.The selection of (hydroxymethyl) phenol used and the performance of composition on the oligomeric condensation product of gained have strong impact and therefore have strong impact on by the described oligomeric condensation product of use as the epoxy system of solidifying agent or promotor gained.
Second composition of condensation product is polyamines.Polyamines can be aliphatic polyamines such as quadrol (EDA), diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), hexamethylene-diamine (HMDA), N-(2-amino-ethyl)-1,3-propylene diamine, two-1, the 3-propylene diamine of N, N'-1,2-ethane two base or dipropylenetriamine, araliphatic polyamines is m-xylene diamine (mXDA) or p-Xylol diamines such as, the two aminocyclohexyl amine (1,3-BAC) of alicyclic polyamine such as 1,3-, isophorone diamine (IPDA) or 4,4'-methylenebiscyclohexylamine, aromatic polyamine such as between phenylenediamine, diaminodiphenyl-methane (DDM) or diamino diphenyl sulfone (DDS), two (the 3-aminopropyl)-2 of heterocyclic polyamines such as N-aminoethyl piperazine (NAEP) or 3,9-, 4, 8,10-tetra-oxa-spiral (5,5) undecane, (wherein alkoxyl group can be oxy ethylene to poly-alkoxy polyamine, oxypropylene, oxidation-1,2-butylidene, oxidation-tetramethylene), or its copolymers is as 4,7-dioxa-1，10-diaminodecane (Jeffamin EDR 176) or 4,7,10-trioxa-1,13-tridecane diamine, 4,7,10-trioxa-1,13-tridecane diamine (ANCAMINE1922A), α-(2-aminomethylethyl)-ω-(2-amino methyl oxyethyl group)-poly-(oxypropylene) (JEFFAMINE D 230, D-400), triethylene glycol diamines and oligopolymer (JEFFAMINE XTJ-504 thereof, JEFFAMINE XTJ-512), two (α, ω-(amino methyl oxyethyl group)-polyoxytrimethylene/altogether-polyoxyethylene (JEFFAMINE XTJ-511), two-(3-aminopropyl) polytetrahydrofuran 350, two-(3-aminopropyl) polytetrahydrofuran 750, poly-(oxidation (methyl isophthalic acid, 2-ethane two base)), based on the polyethers (JEFFAMINE T-403) of the 2-aminopropane end-blocking of propylene oxide and 1,1,1-TriMethylolPropane(TMP) (3:1), and diaminopropyl dipropylene glycol.
Preferred polyamines is such as diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), 1, the two aminocyclohexyl amine (1 of 3-, 3-BAC), isophorone diamine (IPDA), N-aminoethyl piperazine (NAEP), 4,7-dioxadecane-1,10-diamines, 4,9-dioxa dodecane-1,12-diamines, 4,7, the polyamines of 10-trioxa-1,13-tridecane diamine (ANCAMINE 1922A), JEFFAMINED 230, JEFFAMINE D-400, JEFFAMINE XTJ-504 and JEFFAMINE XTJ-511.
In a preferred embodiment, diamines is polyoxyalkylene diamines, and it particularly preferably has based on oxyethane, trimethylene oxide, the unit of two or more mixture of tetrahydrofuran (THF) or these components.Particularly preferably be, polyoxyalkylene diamines is the polyoxyalkylene diamines of general formula I I, and wherein x1 and x2 represents the value of 0 to 70 independently of one another, particularly the value of 1 to 10.The advantage of described polyamines is, it has high molecular and low viscosity.
Further preferably, diamines has the molecular weight in 130 to 500g/Mol scope.Its advantage had is, final product can not be excessively sticky.
Optional composition is phenolic compound, and described phenolic compound has two reactive centers for the reaction of the methylol with (hydroxymethyl) phenol.In category of the present invention, what described reactive center was understood to phenolic compound Reaction Separation can go out the hydrogen of (hydroxymethyl) phenol and the part of hydroxyl (namely as the condensation course of total reaction).Therefore, reactive center is the carbon atom be substituted be combined in aromatic ring of phenolic compound.Preferably, phenolic compound is Resorcinol and/or resorcinol derivatives, dihydroxyphenyl propane or derivatives thereof.
The resorcinol derivatives used in oligomeric condensation product (I) according to the present invention is preferably alkylation Resorcinol, and described alkylation Resorcinol can comprise one or two extra alkyl.Preferably, alkylation Resorcinol is monoalkylation Resorcinol.The present invention is for the not relevant restriction of the substituting group on Resorcinol, but preferably, at least one substituting group on Resorcinol is C1-C12'-alkyl, particularly C1-C8-alkyl.Particularly preferably, the resorcinol derivatives used in oligomeric condensation product is 2-methylresorcinol, 4-butyl Resorcinol and 4-Sucrets.The advantage of resorcinol derivatives is, it additionally raises the concentration of the hydroxyl of the catalytic activity of phenol.
The bisphenol derivative used in oligomeric condensation product (I) according to the present invention is in particular 3,3'-diallyl-4,4'-dihydroxyphenyl propane, 3,3'-dimethyl-4,4'-dihydroxyphenyl propanes, dimethyl bis-phenol P or its mixture.Particularly preferably use 3,3'-diallyl-4,4'-dihydroxyphenyl propane.
The oligomeric condensation product comprising the extra phenolic compound of a part has katalysis strong especially and therefore more preferred than the oligomeric condensation product not comprising Resorcinol within the scope of the invention due to the phenolic group of high density.
Be oligomeric condensation product according to condensation product of the present invention.
Be different from oligomeric condensation product, monomer condenses product is understood to only comprise the product of the compound with single polyamines unit and/or single hydroxymethylbenzyl unit.Therefore in oligomeric condensation product, also there is the compound with at least two hydroxymethylbenzyl unit and at least two polyamines unit.Preferred oligomeric condensation product has mean number at least 1.5 hydroxymethylbenzyl unit and at least 1.5 polyamines unit, particularly at least two hydroxymethylbenzyl unit and at least two polyamines unit, particularly preferably at least 2.5 hydroxymethylbenzyl unit and at least 2.5 polyamines unit.
Oligomeric condensation product according to the present invention comprises oligomeric compound, and described oligomeric compound has the hydroxymethylbenzyl unit number in 1 to 5, preferably 1 to 3 scope, and the diamines number in 2 to 6, particularly 2 to 4 scopes.If oligomeric condensation product additionally comprises phenolic compound unit, then oligomeric condensation product comprises such compound, described compound has the optional phenolic compound unit number in 1 to 5, preferably 1 to 3 scope, and the diamines number in 2 to 6, particularly 2 to 4 scopes.For each unit of phenolic compound, the compound in described condensation product comprises two (hydroxymethyl) phenol units, makes their number in compound be the twice of the unit number of phenolic compound.
The oligomeric condensation product formed by (hydroxymethyl) phenol and polyamines according to the present invention can be obtained by condensation reaction by above-mentioned phenolic compound and polyamines.Condensation product likely obtains according to conventional condensation method, but preferably condensation product obtains according to method as described below.
Another aspect of the invention is the novel method for the preparation of condensation product according to the present invention.The feature of described method is, at least one (hydroxymethyl) phenol as above and at least one polyamines and optionally at least one phenolic compound react and form oligomeric condensation product, and described phenolic compound has two reactive centers of reacting for the methylol with (hydroxymethyl) phenol.
(hydroxymethyl) oxybenzene compound as above can be used as (hydroxymethyl) phenol.Polyamine compounds as above can be used as polyamines.Finally, phenolic compound as above phenolic compound optionally can be used.Thus see above-mentioned embodiment.
In a preferred embodiment, method according to the present invention comprises following method steps:
I () optionally inserts at least one in advance according to (hydroxymethyl) phenol defined above and at least one phenolic compound at the temperature of 15 to 100 DEG C, preferably 20 to 90 DEG C, particularly preferably 20 to 70 DEG C in reaction vessel, described phenolic compound has two reactive centers of reacting for the methylol with (hydroxymethyl) phenol, then temperature is increased to 120 to 190 DEG C, preferably 120 to 180 DEG C, particularly preferably 120 to 170 DEG C
(ii) at the temperature of 15 to 100 DEG C, preferably 20 to 90 DEG C, particularly preferably 20 to 70 DEG C, in reaction vessel, insert at least one (hydroxymethyl) phenol in advance or derive from reaction product and at least one polyamines of (i);
(iii) temperature is increased to 130 to 210 DEG C, preferably 140 to 200 DEG C, particularly preferably 150 to 195 DEG C.
In method, particularly aforesaid method step (i) according to the present invention, raise with temperature afterwards that relevant reaction advantageously carries out 0.5 to 10, the time of preferably 1 to 8 hour, particularly preferably 1 to 5 hour.
Further preferably, according to method of the present invention under inert conditions, particularly carry out under the existence of rare gas element and when getting rid of oxygen.Its advantage had is, the amine of protection sensitivity avoids side reaction.
Be proved to be desirably, the reaction product of at least one (hydroxymethyl) phenol or (hydroxymethyl) phenol and phenolic compound and at least one polyamines react with 3:1 to 1:5, the preferably molar ratio of 1:2 to 1:4, particularly preferably 1:2 to 1:3.
The invention still further relates to the oligomeric condensation product obtained by aforesaid method.
Oligomeric condensation product according to the present invention is particularly suitable as the solidifying agent for amine reactive materials, and described amine reactive materials has at least two amine reactive functional groups.As this amine reactive functional groups, glycidyl ether group and/or isocyanate groups can be considered especially.
In one embodiment of the invention, the amine reactive materials with at least two amine reactive functional groups is diglycidylether.Especially, this material is the diglycidylether of bisphenol-A, bisphenol-f or bisphenol-A/F.Described diglycidylether such as with
gY 250, GY 282 (Huntsman) or D.E.R.
tM331 or D.E.R.
tM330 (Dow) or Epikote828 (Hexion) obtain.
The amine reactive materials that there are at least two amine reactive functional groups by mixing with according to oligomeric condensation product of the present invention, the amido of oligomeric condensation product and the amine reactive functional groups of amine reactive materials react and are cured.
Therefore the present invention be more particularly directed in epoxy-resin systems, such as, in epoxy resin binder and the scope based on the coating of epoxy resin, use the oligomeric condensation product that at least one obtains according to aforesaid method according to oligomeric condensation product of the present invention or at least one.
Especially, oligomeric condensation product according to the present invention for promoting the solidification of epoxy resin binder, for improvement of the adhesivity of epoxy resin binder and/or the stripping strength of epoxy resin binder.
Can use with its former state according to oligomeric condensation product of the present invention or use with composition.
Be used in especially in the curing agent component of two component epoxy compound system according to oligomeric condensation product of the present invention and the oligomeric condensation product according to the present invention that obtained by method according to the present invention.Described oligomeric condensation product can directly to use or composition as curing agent component uses at this.
Particularly preferably, the solidifying agent in bicomponent epoxy resin tackiness agent is used as according to oligomeric condensation product of the present invention.And the two component epoxy compound system of solidification and the product that obtained by it have extremely favourable performance, especially for the solidification promoted rapidly and cold-curing therefore.
When condensation product according to the present invention is for solidifying amine reactive systems, the invention still further relates to the two component combine things comprising the first component K1 and second component K2.First component K1 comprises at least one amine reactive compound, and described amine reactive compound has at least two functional groups can reacted with amine.Second component K2 comprises at least one according to oligomeric condensation product of the present invention.The amine reactive compound with the functional group that at least two can be reacted with amine to describe and above particularly including di-epoxide.
Two kinds of component K1 and K2 can comprise other content well known by persons skilled in the art when needed.Other content this is in particular filler, softening agent, solvent, catalyzer and/or additive.
As filler, particularly preferably carbon black, chalk (particularly through the chalk of coating), sandstone, silicate, light filler such as Ceramic Balls or glass sphere, particularly ceramic hollow ball or glass hollow ball, pyrolytic silicon dioxide and flying dust and composition thereof.
As solvent, be not preferably classified as the solvent of VOC (" volatile organic compounds ").The particularly preferably hydrocarbon of higher such as polyphenylethyl (Solvesso 200; Or alkylated naphthalene CAS64742-94-5).
As the preferred phthalic ester of softening agent and adipic acid ester, particularly Di Iso Decyl Phthalate (DIDP) and Octyl adipate (DOA).
Described pair of component combine thing can be used in different Application Areass.Be preferably used as tackiness agent or sealing agent, in particular as construction adhesive.Have been found that by the attainable performance of condensation product according to the present invention be particularly advantageous in adhesive field.
After the mixing component K1 of described pair of component combine thing and K2 by adhesive application on substrate surface and with another substrate surface close contact.Composition through solidification serves as bonding coat, and described bonding coat can transmit the power between two substrate surfaces of formed complex body.
Two component combine thing is desirably adapted in superstructure and hypogee and in the industry as construction adhesive due to its performance.Such as, this pair of component combine thing, particularly bicomponent epoxy resin composition (namely wherein component K1 comprises diglycidylether) can be used as the tackiness agent of the mixture that binder fibre strengthens.An one example is in reinforcing building, such as, bond carbon fiber layer during bridge fit.
The plastics substrate preparing fibre-reinforced mixture can also be used as according to of the present invention pair of component combine thing, particularly bicomponent epoxy resin composition.Such as carbon fiber or glass fibre can be implanted in two component combine thing and under solid state, such as can be used as fibre composites with the form of laminate.
Similarly, can by two component combine thing, particularly by bicomponent epoxy resin composition in architectural application examples as fiber textile or fiber lay down fabric, and form fibre-reinforced mixture together with building.
According to the polyamines that the viscosity of oligomeric condensation product of the present invention strongly depends on used phenolic compound and uses.Specially suitable oligomeric condensation product according to the present invention has the viscosity being less than 10000mPas at 25 DEG C, thus ensures enough workabilitys.Preferred oligomeric condensation product according to the present invention has the viscosity between 200 and 7000mPas in scope.
It will be clear to someone skilled in the art that can there is a small amount of still unreacted composition when this reaction in final product.
Following invention is explained in detail by following embodiment.
Embodiment
Embodiment 1
Heat in a nitrogen atmosphere with two (the hydroxymethyl)-p-cresol filling container of 180g (0.88Mol) Jeffamin EDR 176 and 99g (0.58Mol) 2,6-.After acquisition uniform mixture (at about 50 DEG C), temperature is increased to 180 DEG C gradually, wherein from the temperature of 160 DEG C, observes constantly boiling.66ml distillment is altogether obtained in the scope of 180 to 178 DEG C.Product is obtained as resistates using the form of sticky yellow transparent polymer.
Embodiment 2
Preset 90g 4,7-dioxas-1，10-diaminodecane and two (the hydroxymethyl)-p-cresols of 60g 2,6-and be heated to the temperature of 178 DEG C gradually in a reservoir.16ml distillment is altogether collected to obtain in the scope of 165 DEG C to 170 DEG C.Product is obtained as resistates using the form of sticky yellow transparent polymer.
Embodiment 3
Two (hydroxymethyl)-p-cresols of preset 120g Jeffamin D 230 and 60g 2,6-and be heated to the temperature of 184 DEG C gradually in a reservoir.Altogether 12ml distillment is obtained at the temperature of 184 DEG C.Product is obtained as resistates using the form of sticky yellow transparent polymer.
Embodiment 4
Preset 120g (1.18 moles) 4 in a reservoir, 9-dioxa-1, two (hydroxymethyl)-p-cresols of 12-dodecamethylene diamine, 20g (0.36 mole) Resorcinol and 60g (0.71 mole) 2,6-and be heated to the temperature of 175 DEG C gradually.Altogether collect to obtain 8ml distillment at such a temperature.Then observe violent viscosity to raise and gelation.Product can not use.
Embodiment 5
Preset 120g (1.18 moles) 4 in a reservoir, 9-dioxa-1, two (hydroxymethyl)-p-cresols of 12-dodecamethylene diamine, 10g (0.18 mole) Resorcinol and 70g (0.83 mole) 2,6-and be heated to the temperature of 173 DEG C gradually.Altogether obtain 10ml distillment at such a temperature.Then observe violent viscosity to raise.Remaining Resorcinol monomer cannot be detected after the reaction mixture was cooled.
Embodiment 6
Preset 120g (1.18 moles) 4 in a reservoir, 9-dioxa-1, two (hydroxymethyl)-p-cresols of 12-n-Laurylamine, 20g (0.35 mole) methyl-m-phenylene diphenol and 60g (0.71 mole) 2,6-and be heated to the temperature of 173 DEG C gradually.Altogether collect to obtain 12ml distillment at such a temperature.Then observe violent viscosity to raise.The residual content of the methylresorcinol monomer being only 0.04% can be determined after the reaction mixture was cooled.
Embodiment 7
Preset 70g (0.45 mole) diallyl bisphenol and two (the hydroxymethyl)-p-cresols of 80g (0.95 mole) 2,6-and be heated to the temperature of 150 DEG C in a reservoir.Altogether collect to obtain 16ml distillment at such a temperature.After the mixture was cooled, the residual content obtaining the diallyl bisphenol of 7.0% is analyzed.
Heat in a nitrogen atmosphere with two (the hydroxymethyl)-p-cresol filling container of 120g N-Jeffamin D230 and 60g 2,6-.Then temperature is increased to 184 DEG C gradually, wherein altogether collects to obtain 12ml distillment.Using the form of viscosity yellow-gray polymkeric substance (as resistates?) obtain product.
Embodiment 4: comparative example 2:
Preset 20g (0.36 mole) Isocenol, 22g 4 in a reservoir, 9-dioxa-1,12-dodecamethylene diamine (1.18 moles) and two (the hydroxymethyl)-p-cresols of 60g (0.71 mole) 2,6-and heat in a nitrogen atmosphere.
Lasting drizzle (Nieseln) is observed from 160 DEG C.At the temperature of 175 DEG C, altogether collect to obtain 8ml distillment, then observe violent viscosity and raise, this causes the gelation of product.The product obtained is not useable for further research.
Embodiment 5
With 10g (0.18 mole) Resorcinol, 120g (1.18 moles) 4,9-dioxa-1,12-dodecamethylene diamine and two (the hydroxymethyl)-p-cresol filling container of 70g (0.83g) 2,6-and heat in a nitrogen atmosphere.After acquisition uniform mixture (at about 115 DEG C), temperature is increased to 173 DEG C gradually, wherein from the temperature of 160 DEG C, observes lasting boiling.10ml distillment and observe violent viscosity and raise altogether is collected to obtain in scope between 170 and 173 DEG C.Obtain transiting product with the form of sticky polymers, described transiting product does not have Resorcinol monomer content.
Embodiment 6
With 20g (0.35 mole) xxx-methylresorcinol, 120g (1.18 moles) 4,9-dioxa-1,12-dodecamethylene diamine and 60g 2, two (the hydroxymethyl)-p-cresol filling container of 6-and heating in a nitrogen atmosphere, is increased to 173 DEG C gradually by temperature after acquisition uniform mixture (at about 110 DEG C).Altogether obtain 12ml distillment at such a temperature, then observe violent viscosity and raise.Using the form of sticky polymers (as resistates?) obtaining product, described product has the methylresorcinol residual content of 0.04%.
Embodiment 7
Two (hydroxymethyl)-p-cresols of preset 70g (0.45 mole) diallyl BPA and 70g 2,6-and be heated to the temperature of about 150 DEG C gradually in a reservoir.After acquisition uniform mixture (at about 130 DEG C), at the temperature of 140 DEG C, observe lasting boiling and altogether obtain 16ml distillment in the scope of 140 to 150 DEG C.Analyze the residual content that the product obtained demonstrates the content of the diallyl BPA of 7.0% ± 0.2 and 2,6-two (hydroxymethyl)-p-cresols of 0.6% ± 0.02 after anneal.
In mixture, add 150g (1.47 moles) 4,9-dioxa-1,12-dodecamethylene diamine and reaction mixture is heated to 173 DEG C.At the temperature of 158 DEG C, observe foaming again and altogether obtain 10ml distillment at the temperature of 173 DEG C.Product obtained after cooling demonstrates the residual content of the diallyl bisphenol of only 1.5% ± 0.1.
Embodiment 8
With 10g (0.18 mole) Resorcinol, 120g (1.09 moles) 4,7,10-trioxa-1,13-tridecane diamine and the two hydroxymethyl-p-cresol filling container of 70g (0.83 mole) 2,6-and heat in a nitrogen atmosphere.After acquisition uniform mixture (at about 120 DEG C), temperature is increased to 178 DEG C gradually, wherein from the temperature of 125 DEG C, observes lasting boiling.12ml distillment is altogether obtained in the scope of 165 to 178 DEG C.Product is obtained as resistates using the form of viscosity transparent polymer.
Embodiment 9
With 25g (0.44 mole) 2-methylresorcinol, 115g (1.05 moles) 4,7,10-trioxa-1,13-tridecane diamine and the two hydroxymethyl-p-cresol filling container of 60g (0.71 mole) 2,6-and heat in a nitrogen atmosphere.After acquisition uniform mixture (at about 110 DEG C), temperature is increased to 176 DEG C gradually, wherein from the temperature of 155 DEG C, observes lasting boiling.11ml distillment is altogether obtained in the scope of 155 to 176 DEG C.Obtain using the form of sticky polymers as resistates and there is redness/beige product.
Embodiment 10
With 50g (0.88 mole) 2-methylresorcinol, 50g pseudocumol is as solubility promoter and two (the hydroxymethyl)-p-cresol filling container of 120g (1.43 moles) 2,6-and heat in a nitrogen atmosphere.At the temperature of 80 DEG C, form the material with flow capacity, and all solids dissolves at the temperature of 120 DEG C.At the temperature of 145 DEG C, composition comes to life and acutely foams, and wherein in the scope of 140 to 145 DEG C, altogether obtains 22ml distillment.According to gpc analysis, resistates has the Mw of 4850 ± 250g/Mol and the Mn of 1420 ± 100g/Mol.
In the second step, in obtained resistates, add 230g (2.09 moles) 4,7,10-trioxa-1,13-tridecane diamine and reaction mixture is heated to 150 DEG C.138ml distillment is altogether obtained when the temperature of 165 to 185 DEG C with when then setting up vacuum.(obtaining as resistates) product have redness/light brown and the 1-methylresorcinol of <0.05%, 2, the 6-dihydroxymethyls-p-cresol of 0.03% ± 0.01% and 1.21% ± 0.03% the residual content of pseudocumol.
Embodiment 11
In a reservoir in a nitrogen atmosphere with stirring heating 50g (0.876 mole) 2-methylresorcinol, 60g ethylene glycol as solubility promoter and 100g (1.19 moles) 2, two (the hydroxymethyl)-p-cresol of 6-, until form perfect solution at the temperature of 105 DEG C.In the temperature range of 140 DEG C to 156 DEG C, altogether obtain 20ml distillment, at the end of distillation, wherein observe violent viscosity raise.In analyzing container, remaining material demonstrates the molecular weight distribution of the content of the 2-methylresorcinol of 0.06% ± 0.01, the content of 2, the 6-dihydroxymethyls-p-cresol of 2.1% ± 0.1 and the Mw=9590 according to GPC.
Embodiment 11
Heat two (the hydroxymethyl)-p-cresol of 50g (0.88 mole) 2-methylresorcinol, 60g ethylene glycol and 100g (1.19 moles) 2,6-in a reservoir in a nitrogen atmosphere.At the temperature of about 5 DEG C, all solids dissolves and comes to life from the temperature of the 156 DEG C mixture that reacts.Then by material cooled to 140 DEG C, wherein altogether 20ml distillment is obtained at such a temperature.According to gpc analysis, resistates (?) there is the Mw of 9590 ± 500g/Mol and the Mn of 1860 ± 100g/Mol.
In the second step, in obtained resistates, add 180g (1.64 moles) 4,7,10-trioxa-1,13-tridecane diamine and reheat reaction mixture.From the temperature of 147 DEG C, observe boiling again and until altogether obtain 120ml distillment at the temperature of 180 DEG C.A 62ml distillment is also obtained after setting up vacuum.The product obtained has the residual content of the ethylene glycol of 1.59% ± 0.08.
Embodiment 12
In a reservoir in a nitrogen atmosphere with stirring heating 60g (0.617 mole) 4-Sucrets, 40g pseudocumol as solubility promoter and 90g (1.07 moles) 2, two (the hydroxymethyl)-p-cresol of 6-, until form perfect solution at the temperature of 80 DEG C.In the temperature range of 130 DEG C to 140 DEG C, altogether obtain 22ml distillment, at the end of distillation, wherein observe violent viscosity raise.In analyzing container, remaining material demonstrates 2, the content of cresorcinol of 9%, the content of 2, the 6-dihydroxymethyls-p-cresol of 10.5% and according to Mw=2370g/Mol ± 100 of GPC and the molecular weight distribution of Mn 1130 ± 100.
In mixture, add 180g (1.64 moles) 4,7,10-trioxa-1,13-tridecane diamine and mixture is heated to 160 DEG C further.Altogether obtain 202ml distillment.The product obtained as resistates has the residual content of pseudocumol of redness/light brown and 0.26% ± 0.1%.
Claims (16)
1. by (hydroxymethyl) phenol of at least one general formula (I), at least one polyamines and the optionally oligomeric condensation product that obtains of at least one phenolic compound
Wherein
R
1represent hydrogen or-CH
3,
R
2expression-CH
2oH, and
R
3represent hydrogen or-CH
3,
Described phenolic compound has two reactive centers of reacting for the methylol with (hydroxymethyl) phenol.
2. oligomeric condensation product according to claim 1, is characterized in that, R
2the ortho position of phenol OH-group is positioned in formula (I).
3. oligomeric condensation product according to claim 1, is characterized in that, R
1and R
3at least one expression-CH
3.
4. the oligomeric condensation product according to any one of claims 1 to 3, it is characterized in that, described polyamines comprises polyoxyalkylene diamines, particularly has the polyoxyalkylene diamines of the unit of two or more the mixture based on oxyethane, trimethylene oxide, tetrahydrofuran (THF) or these components.
5. the oligomeric condensation product according to any one of Claims 1-4, is characterized in that, described polyamines corresponds to formula (II)
Wherein x1 and x2 represents the value of 0 to 70 independently of one another, particularly the value of 1 to 10.
6. the oligomeric condensation product according to any one of claim 1 to 5, is characterized in that, described polyamines has the molecular weight of 130 to 500g/mol.
7. the oligomeric condensation product according to aforementioned any one of claim, it is characterized in that, described phenolic compound is diallyl bisphenol or resorcinol derivatives, particularly alkylation Resorcinol, preferred monoalkylation Resorcinol, and particularly preferably with the Resorcinol that C1-C8-alkyl replaces.
8. prepare the method for oligomeric condensation product, it is characterized in that, (hydroxymethyl) phenol at least one defined according to any one of claims 1 to 3 and at least one polyamines and optionally Resorcinol or at least one resorcinol derivatives or diallyl bisphenol react.
9. method according to claim 8, is characterized in that, uses the polyamines of the definition according to any one of claim 4 to 6.
10. method according to claim 8 or claim 9, is characterized in that, use phenolic compound according to claim 7.
Method described in 11. any one of according to Claim 8 to 10, comprises following method steps:
(i) (hydroxymethyl) phenol that optionally preset at least one defines according to any one of claims 1 to 3 in reaction vessel at the temperature of 15 to 100 DEG C, preferably 20 to 90 DEG C, particularly preferably 20 to 70 DEG C and at least one phenolic compound, described phenolic compound has two reactive centers of reacting for the methylol with (hydroxymethyl) phenol, then temperature is increased to 120 to 190 DEG C, preferably 120 to 180 DEG C, particularly preferably 120 to 170 DEG C
(ii) (hydroxymethyl) phenol that preset at least one defines according to any one of claims 1 to 3 in reaction vessel at the temperature of 15 to 100 DEG C, preferably 20 to 90 DEG C, particularly preferably 20 to 70 DEG C or the reaction product deriving from (i) and at least one polyamines
(iii) temperature is increased to 130 to 210 DEG C, preferably 140 to 200 DEG C, particularly preferably 150 to 195 DEG C.
12. methods according to claim 11, is characterized in that, in the optional step (i) of method, the rising of temperature is carried out 0.5 to 10 hour, preferably 1 to 8 hour, the particularly preferably time of 1 to 5 hour.
Method described in 13. any one of according to Claim 8 to 12, it is characterized in that, the reaction product of described at least one (hydroxymethyl) phenol or (hydroxymethyl) phenol and phenolic compound and at least one polyamines react with 3:1 to 1:5, the preferably molar ratio of 1:2 to 1:4, particularly preferably 1:2 to 1:3.
14. condensation products obtained by the method described in any one of according to Claim 8 to 13.
15. at least one according to any one of claim 1 to 7 or condensation product according to claim 14 at epoxy-resin systems, the purposes particularly in epoxy resin binder and epoxypaint.
16. pairs of component combine things, described pair of component combine thing comprises the first component K1 and second component K2, described first component K1 comprises at least two functional groups can reacted with amine, and described second component K2 comprises at least one according to any one of claim 1 to 7 or condensation product according to claim 14.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12159490.7 | 2012-03-14 | ||
| EP12159490.7A EP2639252A1 (en) | 2012-03-14 | 2012-03-14 | Polymeric accelerator for two component epoxy resin |
| PCT/EP2013/055281 WO2013135839A1 (en) | 2012-03-14 | 2013-03-14 | New reactive polymer catalysts for 2-component epoxy resin systems |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104411736A true CN104411736A (en) | 2015-03-11 |
| CN104411736B CN104411736B (en) | 2017-06-09 |
Family
ID=47901979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380013786.4A Expired - Fee Related CN104411736B (en) | 2012-03-14 | 2013-03-14 | For the novel chemically-reactive polyalcohol catalyst of bicomponent epoxy resin system |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US9163112B2 (en) |
| EP (2) | EP2639252A1 (en) |
| JP (1) | JP6392126B2 (en) |
| KR (1) | KR102131186B1 (en) |
| CN (1) | CN104411736B (en) |
| CA (1) | CA2866760C (en) |
| WO (1) | WO2013135839A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104457752A (en) * | 2014-11-28 | 2015-03-25 | 英业达科技有限公司 | Motion trail sensing and measurement system and motion trail collection method thereof |
| KR20240153619A (en) | 2017-08-31 | 2024-10-23 | 메탈렌츠 인코포레이티드 | Transmissive metasurface lens integration |
| WO2019147828A1 (en) * | 2018-01-24 | 2019-08-01 | President And Fellows Of Harvard College | Polarization state generation with a metasurface |
| EP4004608A4 (en) | 2019-07-26 | 2023-08-30 | Metalenz, Inc. | Aperture-metasurface and hybrid refractive-metasurface imaging systems |
| WO2023286081A1 (en) | 2021-07-13 | 2023-01-19 | Elantas Beck India Limited | Epoxy modified resin |
| US11927769B2 (en) | 2022-03-31 | 2024-03-12 | Metalenz, Inc. | Polarization sorting metasurface microlens array device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4259464A (en) * | 1971-08-18 | 1981-03-31 | Petrolite Corporation | Cyclic phenol-aldehyde resins |
| JP2001106783A (en) * | 1999-10-01 | 2001-04-17 | Arakawa Chem Ind Co Ltd | Phenol resin composition and curing agent for epoxy resin |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3624314A1 (en) | 1986-07-18 | 1988-01-28 | Hoechst Ag | USE OF EPOXY RESIN / HARDENER BLENDS FOR PRODUCING COATINGS WITH INCREASED INTERLAYER LIABILITY |
| US4786683A (en) * | 1987-05-26 | 1988-11-22 | The Firestone Tire & Rubber Company | Phenolic resin and polyether treated guayule resin |
| US4837121A (en) * | 1987-11-23 | 1989-06-06 | Olin Hunt Specialty Products Inc. | Thermally stable light-sensitive compositions with o-quinone diazide and phenolic resin |
| FR2728064A1 (en) | 1994-12-12 | 1996-06-14 | Giat Ind Sa | SEALING DEVICE FOR FIREARMS HAVING AMMUNITION WITHOUT SOCKET |
| DE19632749A1 (en) * | 1996-08-14 | 1998-02-19 | Hoechst Ag | Hardening component for epoxy resins and their use |
| JP4411571B2 (en) | 1998-09-14 | 2010-02-10 | ハンツマン アドバンスト マテリアルズ （スイッツァランド） ゲーエムベーハー | Accelerator for curable systems |
| US6916550B2 (en) | 2000-09-11 | 2005-07-12 | Allison Advanced Development Company | Method of manufacturing a metal matrix composite structure |
| US6987161B2 (en) * | 2000-11-16 | 2006-01-17 | Ardes Enterprise, Inc. | Epoxy hardeners for low temperature curing |
| US6491845B1 (en) * | 2000-11-16 | 2002-12-10 | Richard D. Schile | Epoxy hardener of phenolic or 2° OH polyol and methylol polyol |
| EP1475411A1 (en) | 2003-05-05 | 2004-11-10 | Sika Technology AG | Mannich bases and Preparation of Mannich bases |
| EP1475412A1 (en) | 2003-05-05 | 2004-11-10 | Sika Technology AG | Epoxy compositions containing a Mannich base suitable for high temperature applications |
| EP1717253A1 (en) | 2005-04-29 | 2006-11-02 | Sika Technology AG | Mannich base based on resorcinol |
-
2012
- 2012-03-14 EP EP12159490.7A patent/EP2639252A1/en not_active Withdrawn
-
2013
- 2013-03-14 CA CA2866760A patent/CA2866760C/en not_active Expired - Fee Related
- 2013-03-14 WO PCT/EP2013/055281 patent/WO2013135839A1/en active Application Filing
- 2013-03-14 CN CN201380013786.4A patent/CN104411736B/en not_active Expired - Fee Related
- 2013-03-14 KR KR1020147026153A patent/KR102131186B1/en active IP Right Grant
- 2013-03-14 US US14/382,236 patent/US9163112B2/en not_active Expired - Fee Related
- 2013-03-14 JP JP2014561456A patent/JP6392126B2/en not_active Expired - Fee Related
- 2013-03-14 EP EP13710832.0A patent/EP2825580B1/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4259464A (en) * | 1971-08-18 | 1981-03-31 | Petrolite Corporation | Cyclic phenol-aldehyde resins |
| JP2001106783A (en) * | 1999-10-01 | 2001-04-17 | Arakawa Chem Ind Co Ltd | Phenol resin composition and curing agent for epoxy resin |
Also Published As
| Publication number | Publication date |
|---|---|
| US20150018500A1 (en) | 2015-01-15 |
| JP2015515511A (en) | 2015-05-28 |
| CN104411736B (en) | 2017-06-09 |
| EP2825580B1 (en) | 2020-09-02 |
| KR20140143760A (en) | 2014-12-17 |
| CA2866760A1 (en) | 2013-09-19 |
| CA2866760C (en) | 2020-10-27 |
| EP2825580A1 (en) | 2015-01-21 |
| KR102131186B1 (en) | 2020-07-08 |
| EP2639252A1 (en) | 2013-09-18 |
| WO2013135839A1 (en) | 2013-09-19 |
| US9163112B2 (en) | 2015-10-20 |
| JP6392126B2 (en) | 2018-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101353813B1 (en) | Benzylated polyalkylene polyamines and uses thereof | |
| CN104411736A (en) | New reactive polymer catalysts for 2-component epoxy resin systems | |
| JP5491872B2 (en) | High-functional amine compounds and methods of use thereof | |
| US20100280185A1 (en) | Highly-branched melamine polymers | |
| KR101562421B1 (en) | Mixtures of amines having guanidine derivatives | |
| EP2758446B1 (en) | Benzylated polyamine curing agents | |
| JP6865731B2 (en) | Use of oligo-N, N-bis- (3-aminopropyl) methylamine as a curing agent for epoxy resins | |
| US8247517B2 (en) | Catalyst for curing epoxides | |
| EP3680270A1 (en) | Mono-alkylated diamines for epoxy formulations: novel curing agents for epoxy systems | |
| MX2015003495A (en) | Curable epoxy resin composition. | |
| US9650542B2 (en) | Use of polypropyleneimine as curing agent for epoxide resins | |
| CN105637002B (en) | The ether amines of thermal stability with enhancing and their purposes as curing agent or Macroscopic single crystal intermediate | |
| JP6117700B2 (en) | Condensation products of amino functional polymers | |
| CN118119659A (en) | Flame-retardant epoxy resin composition | |
| JP6136245B2 (en) | Amine composition for epoxy curing agent | |
| JP6813562B6 (en) | Curable composition | |
| CN116848086A (en) | Composition containing phenolic amine and preparation method thereof | |
| CN111511795B (en) | Benzylated triaminobonanes and uses thereof | |
| EP4308625A1 (en) | Amine-terminated oxamide curatives | |
| EP4442726A1 (en) | Multi-component epoxy resin composition with accelerated curing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170609 Termination date: 20210314 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |